U.S. patent number 4,859,458 [Application Number 07/173,519] was granted by the patent office on 1989-08-22 for hair conditioning polymers containing alkoxylated nitrogen salts of sulfonic acid.
This patent grant is currently assigned to Morton Thiokol, Inc.. Invention is credited to Ann B. Salamone, Susan L. Snyder.
United States Patent |
4,859,458 |
Salamone , et al. |
August 22, 1989 |
**Please see images for:
( Certificate of Correction ) ** |
Hair conditioning polymers containing alkoxylated nitrogen salts of
sulfonic acid
Abstract
Polymers containing alkoxylated nitrogen salts of sulfonic acid
are useful for imparting good conditioning properties such as
combability, feel, manageability, and curl retention to hair. The
polymers may also comprise neutral, anionic, and/or cationic
monomers.
Inventors: |
Salamone; Ann B. (Marblehead,
MA), Snyder; Susan L. (Beverly, MA) |
Assignee: |
Morton Thiokol, Inc. (Chicago,
IL)
|
Family
ID: |
26869240 |
Appl.
No.: |
07/173,519 |
Filed: |
March 25, 1988 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
|
302329 |
Sep 15, 1981 |
|
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|
Current U.S.
Class: |
424/70.15;
424/70.16; 424/70.17; 526/287; 526/310 |
Current CPC
Class: |
A61K
8/45 (20130101); A61K 8/731 (20130101); A61K
8/8158 (20130101); A61K 8/90 (20130101); A61Q
5/12 (20130101); C08F 246/00 (20130101) |
Current International
Class: |
A61K
8/45 (20060101); A61K 8/73 (20060101); A61K
8/72 (20060101); A61K 8/81 (20060101); A61K
8/90 (20060101); A61K 8/30 (20060101); A61Q
5/12 (20060101); C08F 246/00 (20060101); A61K
007/06 (); A61K 007/08 (); A61K 007/11 (); A61K
009/10 () |
Field of
Search: |
;424/70
;526/287,310 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Primary Examiner: Ore; Dale R.
Attorney, Agent or Firm: White; Gerald K.
Parent Case Text
This is a continuation of co-pending application Ser. No. 302,329
filed on Sept. 15, 1981, now abandoned.
Claims
We claim:
1. A polyanionic polymer for imparting good conditioning properties
to hair made from an ethylenically unsaturated addition
polymerizable monomer containing an alkyloxylated nitrogen salt of
sulfonic acid, and at least one additional monomer selected from
the group consisting of neutral monomers, anionic monomers, or
cationic monomers; said addition polymerizable monomer being
present in a mole fraction of about 0.03 to 1.0; said salt being
derived from an ethoxylated amine having the following structure:
##STR15##
2. The polymer of claim 1, wherein: said polymerizable monomer
comprises at least one ethylenically unsaturated addition
polymerizable monomer containing an ethoxylated nitrogen salt of
sulfonic acid.
3. The polymer of claim 1, wherein: said additional monomer is a
neutral monomer and is a member selected from the group consisting
of acrylamide, substututed acrylamide, vinyl acetate, vinyl
pyrrolidone, N-vinyl acetamide, ethylene, styrene, acrylate, and
admixtures thereof.
4. The polymer claim 1, wherein: said second monomer is an anionic
monomer and is a member selected from the group consisting of
acrylic acid, maleic acid, maleic acid esters, crotonic acid, vinyl
phosphonate, and admixtures thereof.
5. The polymer of claim 1, wherein: said second monomer is a
cationic monomer and is a member selected from the group consisting
of vinyl amine, dimethylamino-ethyl methacrylate, vinyl pyridine,
dimethyl diallyl ammomium chloride, methacrylamido propyl trimethyl
ammonium chloride, vinyl benzyl trimethyl ammonium chloride, vinyl
triphenylphosphonium bromide, and admixtures thereof.
6. The polymer of claim 1, wherein: said polymerizable monomer
comprises 2-acrylamido 2-methyl propane sulfonate.
7. The polymer of claim 6, wherein: said additional monomer
comprises acrylamide.
8. The polymer of claim 7, wherein: said salt comprises soya
bis(polyoxyethylene).sub.15 amine.
9. The polymer of claim 8, wherein: said salt is present in a mole
fraction of about 0.1 to 1.0.
10. The polymer of claim 9, wherein: said salt is present in a mole
fraction of about 0.4 to 0.6.
11. The polymer of claim 1, wherein: said salt comprises soy
bis(polyoxyethylene).sub.15 amine.
12. The polymer of claim 1, wherein: said salt comprises
cetyl-stearyl bis(polyoxyethylene).sub.7.5 amine.
13. The polymer of claim 1, wherein: said salt comprises
cetyl-stearyl bis(polyoxyethylene).sub.25 amine.
14. The polymer of claim 1, wherein: said salt comprises tallow
bis(polyoxyethylene).sub.7.5 amine.
15. The polymer of claim 1, wherein: said salt comprises stearyl
bis(polyoxyethylene).sub.7.5 amine.
16. The polymer of claim 1, wherein: said salt comprises stearyl
bis(polyoxyethylene).sub.25 amine.
17. The polymer of claim 1, wherein: said salt comprises coco
bis(polyoxyethylene).sub.7.5 amine.
18. The polymer of claim 1, wherein: said ethoxylated amine
comprises tallow poly(oxyethylene).sub.x amine.
19. The polymer of claim 1, wherein: said ethoxylated amine has the
following structure: ##STR16##
20. The polymer of claim 1, wherein: said ethoxylated amine
comprises soya bis(polyoxyethylene).sub.x amine.
21. The polymer of claim 1, wherein: said ethoxylated amine
comprises coco bis(polyoxyethylene).sub.x amine.
22. The polymer of claim 1, wherein: said ethoxylated amine
comprises oleyl bis(polyoxyethylene).sub.x amine.
23. The polymer of claim 1, wherein: said ethoxylated amine
comprises cetyl-stearyl bis(polyoxyethylene).sub.x amine.
24. The polymer of claim 1, wherein: said ethoxylated amine
comprises tallow poly(oxyethylene).sub.x amine.
25. A hair conditioning product containing the polymer of claim 10
in an amount from 0.1 to 10 wt. %.
26. A method of conditioning hair, comprising applying a
composition comprising the product of claim 25 to hair so as to
obtain good hair conditioning properties.
27. A polyanionic polymer for imparting good conditioning
properties to hair made from an ethylenically unsaturated addition
polymerizable monomer being present in a mole fraction of about
0.03 to 1.0 and containing an alkoxylated nitrogen salt of sulfonic
acid; said salt being derived from an ethoxylated quaternary
ammonium salt having the following structure: ##STR17##
28. The polymer of claim 27, wherein: said polymer includes at
least one additional monomer selected from the group consisting of
neutral monomers, anionic monomers, cationic monomers, or
admixtures thereof.
29. The polymer of claim 27, wherein: said polymerizable monomer
comprises at least one ethylenically unsaturated addition
polymerizable monomer containing an ethoxylated nitrogen salt of a
sulfonic acid.
30. The polymer of claim 28, wherein: said polymerizable monomer
comprises at least one ethylenically unsaturated addition
polymerizable monmomer containing an ethoxylated nitrogen salt of a
sulfonic acid.
31. The polymer of claim 28, wherein: said additional monomer is a
neutral monomer and is a member selected from the group consisting
of acrylamide, substituted acrylamide, vinyl acetate, vinyl
pyrrolidone, N-vinyl acetamide, ethylene, styrene, acrylate, and
admixtures thereof.
32. The polymer of claim 28, wherein: said second monomer is an
anionic momomer and is a member selected from the group consisting
of acrylic acid, maleic acid, maleic acid esters, crotonic acid,
vinyl phosphonate and admixtures thereof.
33. The polymer of claim 28, wherein: said second monomer is a
cationic monomer and is a member selected from the group consisting
of vinyl amine, dimethylamino-ethyl methacrylate vinyl pyridine,
dimethyl diallyl ammonium chloride, methacrylamido propyl trimethyl
ammonium cloride, vinyl benzyl trimethyl ammonium chloride, vinyl
triphenylphosphonium bromide, and admixtures thereof.
34. The polymer of claim 28, wherein: said polymerizable monomer
comprises 2-acrylamido 2-methyl propane sulfonate.
35. The polymer of claim 34, wherein: said additional monomer
comprises acrylamide.
36. A hair conditioning product containing the polymer of claim
35.
37. A method of conditioning hair, comprising applying a
composition comprising the product of claim 36 to hair so as to
obtain good hair conditioning properties.
38. The polymer of claim 27, wherein: said alkoxylated quaternary
ammonium salt comprises methyl bis(2-hydroxyethyl) coco ammonium
salt.
39. The polymer of claim 27, wherein: said alkoxylated quaternary
ammonium salt comprises ethyl bis(polyhydroxyethyl) alkyl ammonium
salt.
40. The polymer of claim 27, wherein: said alkoxylated quaternary
ammonium salt comprises stearyl tris(2-hydroxyethyl) ammonium
salt.
41. The polymer of claim 27, wherein: said alkoxylated quaternary
ammonium salt comprises stearyl, hydroxyethyl bis(polyhydroxyethyl)
ammonium salt.
42. The polymer of claim 27, wherein: said alkoxylated quaternary
ammonium salt comprises cetyl, stearyl tris(polyhydroxyethyl)
ammonium salt.
43. A hair conditioning product being a member selected from the
group consisting of shampoo, and conditioner: said product
containing from 0.1 to 10 wt. % of a polyanionic polymer made from
an ethylenically unsaturated addition polymerizable monomer
containing an alkoxylated nitrogen salt of sulfonic acid; said
addition polymerizable monomer being present in a mole fraction of
about 0.3 to 1.0; said salt being derived from an ethoxylated amine
having the following structure: ##STR18## said product having the
properties of imparting excellent combability, feel, manageability,
and curl retention to hair and minimizing static flyaway.
44. A method of conditioning hair, comprising applying the product
of claim 43 to hair.
45. A hair conditioning product being a member selected from the
group consisting of shampoo, and conditioner; said product
containing from 0.1 to 10 wt. % of polyanionic polymer made from an
ethylenically unsaturated addition polymerizable monomer containing
an alkoxylated nitrogen salt of sulfonic acid; said addition
polymerizable monomer being present in a mole fraction of about
0.03 to 1.0; said salt being derived from an ethoxylated quaternary
ammonium salt having the following structure: ##STR19## said
product having the properties of imparting excellent combability,
feel, manageability, and curl retention to hair and minimizing
static flyaway.
46. A method of conditioning hair, comprising applying the product
of claim 45 to hair.
Description
BACKGROUND OF THE INVENTION
This invention generally pertains to a polymer useful for imparting
good conditioning properties to hair. The polymer comprises an
ethylenically unsaturated addition polymerizable monomer containing
an alkoxylated nitrogen salt of sulfonic acid. The polymers may
also include neutral, anionic and/or cationic monomers. Hair
conditioning products generally are considered to function to
improve such properties as fuel, wet and dry combability, luster,
curl retention, as well as to minimize static flyaway, mend split
ends, and decrease drying and defatting caused by cleaning
products. Hair conditioners are routinely incorporated into such
products as shampoos, creme rinses, hair colorants, hair
straighteners, and hair curlers.
In the past, three types of compounds have been commonly
incorporated into hair conditioning products. They are cationic
polymers, proteins or protein derivatives, and fatty quaternary
ammonium compounds. Commonly used cationic polymers include:
quaternary nitrogen-containing hydroxyethyl cellulose compounds,
copolymers of vinylpyrrolidone and dimethylamino ethyl
methacrylate, and amino functional polydimethyl-siloxane.
Hydrolyzed animal protein has been frequently used as a
conditioner. Also used are natural products such as collagen and
casein. Suitable quaternary ammonium compounds include such
products as stearyl dimethyl ammonium chloride.
U.S. Pat. Nos. 4,065,422 and 4,128,631 are directed to personal
care products which serve to impart a feeling of lubricity. These
homopolymer products contain high molecular weight polymeric salts
of 2-acrylamido-2-methylpropane sulfonic acid (AMPS). Such AMPS
homopolymers have a molecular weight ranging from 1 to 5 million.
Another high molecular weight sulfonate-containing homopolymer,
marketed by National Starch and Chemical Corporation under the
trademark "FLEXAN", is recommended for use in hair conditioners and
setting lotions. This highly anionic additive is described as a
polystyrene sulfonate, sodium salt, supplied as an aqueous solution
at 30% solids. In addition, U.S. Pat. No. 3,937,802 discloses a
hydrophilic polymer having at least 3 wt % sulfonate groups. Such
polymer is disclosed to be useful for promoting curl retention when
included in hair sprays. U.S. Pat. No. 4,210,161 discloses a creme
rinse composition which is stated to provide for ease of combing,
static control, body and setting properties. The product is an
aqueous composition containing 0.02 to 2 wt % of an anionic polymer
and 0.1 to 5 wt % of a cationic surfactant capable of forming a
water insoluble product.
The polymer of the invention is believed to constitute a very
significant improvement in the hair conditioning art because such
polymer, when contrasted to the products mentioned above, exhibits
a superior combination of hair care properties. These properties
include wet and dry combability, feel and fly away control. The
extent of the improvement will become more apparent during later
portions of this disclosure.
SUMMARY OF THE INVENTION
The polymer of the invention has been found to impart excellent
combability, feel, manageability, and curl retention to hair and to
minimize static flyaway. In addition, such polymers are also useful
for imparting anti-static properties to materials susceptible to
the build-up of static electricity such as photographic films,
plastic forms, carpeting, paper, and fabrics such as clothing.
These polymers are generally classified as polyanionics; i.e.
polymers which contain sulfonic acid groups neutralized with an
alkoxylated nitrogen-containing compound. Such alkoxylated
nitrogen-containing compound may conveniently be an ethoxylated
amine or ethoxylated quaternary ammonium salt. The polymer includes
at least one ethylenically unsaturated addition polymerizable
monomer containing an alkoxylated nitrogen salt of sulfonic acid
and may also include additional monomers that may be neutral,
anionic and/or cationic.
Sulfonic acid containing polymers as described herein are
neutralized with ethoxylated quaternary ammonium salt or
ethoxylated amines to form the desired polymer of the invention.
Neutralization may be effected to proportions between about 10 to
100 mole % to be employed in the practice of the invention. A range
of about 25 to 100 mole % is preferred. Neutralization with an
ethoxylated quaternary ammonium salt is generally depicted as
follows: ##STR1## Neutralization with an ethoxylated amine is
generally depicted as follows: ##STR2##
A concentration range of from about 0.1 to 10 wt % of the polymer
of the invention has been found to be useful in hair conditioning
shampoos and the like. A concentration on the order of about 0.5 wt
% is preferred. For other types of hair care formulations, the
amount required will vary depending upon the type of treatment and
quality of the hair.
Nitrogen salts of sulfonic acids include alkoxylated quaternary
ammonium salts, alkoxylated amines and admixtures thereof.
Quaternary ammonium salts suitable for use in the invention have
the following general structure: ##STR3##
Suitable examples of alkoxylated quaternary ammonium salts include:
##STR4##
Alkoxylated amines suitable for use in the invention have the
following general structure: ##STR5##
As may be seen from the extremes of Examples 16-30, X in the above
formula ranges from 7.5 to 25. This supports the following formula:
##STR6##
Suitable examples of alkoxylated amines include the following
compounds: ##STR7##
Soya bis(polyoxyethylene).sub.15 amine is an example of a
particularly suitable ethoxylated amine salt.
Although the polymer of the invention may consist entirely of the
product produced by the polymerization of ethylenically unsaturated
monomer containing an alkoxylated nitrogen salt of sulfonic acid,
an additional monomer may be utilized. The additional monomer (or
monomers) does not add or detract from the unique properties and
advantages of the sulfonic acid type polymer, but is utilized to
reduce the cost of the polymer. Such polymers may be produced
through vinyl polymerization monomers containing sulfonate. Such
monomers include 2-acrylamido-2-methyl propane sulfonate, ethylene
sulfonate, sulfoethyl methacrylate and styrene sulfonate.
Structures for these monomers are shown as follows: ##STR8##
Other suitable polymers may be produced by polymer derivitization
to obtain a sulfonate-containing polymer as shown below:
##STR9##
As stated above, the monomers containing nitrogen salts of sulfonic
acid may optionally be polymerized with a second monomer. Such
second monomer may be neutral, anionic, or cationic.
Suitable neutral monomers include acrylamide, substituted
acrylamide, vinyl acetate, polyvinyl alcohol derived by hydrolysis
of polyvinyl acetate, vinyl pyrrolidone, N-vinyl acetamide,
ethylene, styrene, acrylates, methacrylates and admixtures thereof.
Suitable acrylamides are set forth below: ##STR10##
Suitable neutralized anionic monomers include acrylic acid,
methacrylic acid, maleic acid, maleic acid esters, crotonic acid,
vinyl phosphonate and admixtures thereof. Structures of several
anionic monomers are set forth below: ##STR11##
Suitable cationic monomers include vinyl amine, dimethylamino-ethyl
methacrylate, vinyl pyridine, dimethyl diallyl ammonium chloride,
methacrylamido propyl trimethyl ammonium chloride, vinyl benzyl
trimethyl ammonium chloride, vinyl triphenyl phosphonium bromide,
and admixtures thereof. Structures of several cationic monomers are
set forth below: ##STR12##
The polymers may be not only linear, but also may be segmental in
nature. Multi-functional vinyl monomers, such as divinyl benzene or
methylene bis acrylamide, may be used to promote branching of the
sulfonate-containing polymers. Grafting of the sulfonate-containing
monomers onto natural or synthetic polymers can be initiated by the
use of ceric ammonium nitrate or benzoyl peroxide, for instance. A
third approach would be to synthesize block copolymers which can be
formed by the use of bifunctional initiators, e.g., di-t-butyl
4,4'-azobis(4-cyanoperoxyvalerate); or ceric ammonium
nitrate-treated polyvinyl pyrrolidone (PVP) which results in
triblock polymers, PVP being the center block.
The molecular weight of these polymers may be controlled by varying
the amount of initiator, which could be any free radical initiator,
such as ammonium persulfate, plus redox catalysts, if desired, or
azobis-isobutyro nitrile (AIBN); by varying the amount of chain
transfer agent such as FeCl.sub.3, NaHSO.sub.3, mercaptan, etc.; or
by varying the temperature of reaction. The polymerization itself
can be achieved by solution, suspension, or emulsion
techniques.
The polymers composed of alkoxylated nitrogen salts of sulfonic
acid containing monomers and the additional monomer may be of
various mole ratios. Suitable ratios are from about 0.03 to 1.0 of
the sulfonic acid monomers with the ethoxylated amine salt being
present in a mole fraction of about 0.1 to 1.0. The preferred
polymer of the invention is poly(acrylamide-(co-AMPS) in a mole
fraction of 9 acrylamide-1 Amps., which has been partially
neutralized with soya bis(polyoxyethylene).sub.15 amine. Such
polymer is preferred because its addition leads to superior wet
combility, dry combability, feel, and anti-stat properties.
To be useful as hair conditioners, the strong acid-containing
polymers should not be in the free acid form. Several salts have
demonstrated usefulness, e.g., ethoxylated quaternary ammonium and
ethoxylated amine salts. Neutralization (10 to 100 mole %) of
sulfonic acid containing polymer with an ethoxylated nitrogen
containing salt has proven especially beneficial for improving hair
conditioning properties; with 40 to 60 mole % being preferred to
further optimize hair conditioning properties.
The following examples and test results are believed to demonstrate
the practice of the invention as well as demonstrate the
superiority of the polymer when contrasted with other polymeric
hair care additives.
EXAMPLE 1
A 22 liter four-neck flask fitted with reflux condenser, nitrogen
purge, thermocouple, and stirrer was charged with 3,750 g (18.12
moles) of 2-acrylamido-2-methyl propane sulfonic acid (AMPS) from
Lubrizol predissolved in 3,875 g of deionized water containing
0.375 g of CuSO.sub.4.5H.sub.2 O (0.0015 m) and N.sub.2 purged. In
rapid succession, the following were added with stirring at room
temperature: 225 g of (NH.sub.4).sub.2 S.sub.2 O.sub.8 (0.986)
predissolved in 2,250 ml of H.sub.2 O, 0.375 g of
FeSO.sub.4.7H.sub.2 O (0.0013 m) predissolved in 125 ml of H.sub.2
O, and 375 g of NaHSO.sub.3 (3.6 m) predissolved in 750 ml of
H.sub.2 O, and an additional 1,125 ml of H.sub.2 O. After 15
minutes, polymerization began as indicated by a 25.degree. C.
exotherm (20.degree. C. to 45.degree. C.). After 6 hours, the
reaction product was neutralized with 750 g of NaOH (18.75 m)
predissolved in 750 ml of H.sub.2 O. The product obtained was a
clear yellow liquid having a Brookfield viscosity (#3, 6 rpm) of
1,400 cp. at 35% polymer solids. Infrared spectrum confirmed the
structure as poly(AMPS) with absorptions at 1650 cm.sup.-1, 1500
cm.sup.-1, 1220 cm.sup.-1, 1035 cm.sup.-1, and 615 cm.sup.-1.
EXAMPLE 2
52.2 g of NaOH (1.3 m) was dissolved in 1,000 g of deionized
H.sub.2 O and 270 g of AMPS (1.3 m) was added to it, with cooling.
This solution was charged to a 3-liter resin flask equipped with
stirrer, condenser, thermocouple and N.sub.2 purge. After purging
the system with N.sub.2, 5.4 g of (NH.sub.4).sub.2 S.sub.2 O.sub.8
(0.024 m) and 0.0202 g of FeCl.sub.3 (75 ppm) were added. Deionized
H.sub.2 O was added to bring the solids content to 15% (w/w). The
solution was heated to 84.+-.2.degree. C. and held for 4 hours.
After 1.5 hours, 6.78 g of NaHSO.sub.3 (0.013 m) was added. The
product obtained was a clear viscous liquid. Infrared spectrum
confirmed polymer structure.
EXAMPLE 3
A 500 ml 4-neck resin kettle fitted with a thermocouple, reflux
condenser, N.sub.2 purge, and stirrer was charged with 18.63 g of
AMPS (0.09 m) predissolved in 250 ml of deionized H.sub.2 O and
neutralized with 4 g of NaOH (0.1 m). While N.sub.2 purging, 0.87 g
of NH.sub.4 lauryl sulfate (1 phm), and 0.87 g NaH.sub.2 PO.sub.4
(1 phm) predissolved in 38 ml DI H.sub.2 O, and 0.42 g of AIBN (0.5
phm) were added. After thorough mixing, 68.8 g of vinyl acetate
(0.8 m) was added and a suspension formed. The reaction temperature
was maintained at 40.degree. C. for 17 hours. A white latex was
formed. The product was composed of 6 moles vinyl acetate/1 mole
AMPS according to C, H, N analysis.
EXAMPLE 4
Hydrolysis of poly(vinyl acetate-(co)-AMPS (Example 3) to the free
alcohol was accomplished by the addition of 3 g of 95% H.sub.2
SO.sub.4 and a reaction temperature of 98.degree. C. was maintained
for 8 hours. As hydrolysis progressed, the polymer became more
water soluble. The product was a white translucent viscous liquid.
Infrared spectrum confirmed polymer structure.
EXAMPLE 5
A 250 ml 3-necked round bottom flask equipped with air condenser,
CaCl.sub.2 drying tube, and thermocouple was charged with 13.2 g of
poly(AMPS-Na) (0.058 m) and 13.44 g of PCl.sub.5 (0.0645 m) which
were mixed as solids. The mixture was heated for 1 hour at
110.degree. C., washed with dried diethyl ether and then dried
under vacuum. The resultant light brown product was then mixed with
15.66 g of octadecyl amine (0.058 m) in a 250 ml round bottom flask
and heated to 100.degree. C. for 30 minutes. The reaction product
was washed with dried diethyl ether and water. The desired
polymeric product was retained in the water phase which was light
amber in color. C, H, N analysis confirmed polymer structure.
EXAMPLE 6
394 g AMPS (1.9 m) was neutralized, with cooling, with 76.2 g NaOH
(1.9 m) in 1125 ml deionized H.sub.2 O. 14.9 g acrylamide (0.21 m)
was dissolved in 100 ml H.sub.2 O. Both monomer solutions were
added to a 3-liter resin flask equiped with a reflux condenser,
overhead air-driven stirrer, nitrogen inlet and thermocouple. The
system was purged with N.sub.2. 8 g ammonium persulfate (0.035 m)
in 300 ml H.sub.2 O was added. The solution was heated to
80.degree. C. and held for 6 hours. After 1 hour, 400 ml of H.sub.2
O was added. After 3 hours, 4.09 g (NH.sub.4).sub.2 S.sub.2 O.sub.8
(0.0179 m) and 10.23 g NaHSO.sub.3 (0.098 m) were added in 70 ml of
H.sub.2 O. After 5 hours, another 4.09 g of (NH.sub.4).sub.2
S.sub.2 O.sub.8 and 8.18 g of NaHSO.sub.3 (0.078 m) in 70 ml of
H.sub.2 O were added. The product was a pale yellow solution. C, H,
N analysis confirmed with the comonomer ratio was 9/1.
EXAMPLE 7
40 g of NaOH (1 m) was dissolved in 1,000 g of deionized H.sub.2 O.
207 g of 2-acrylamido-2-methylpropane sulfonic acid (1 m) was added
to the NaOH solution, followed by addition of 23.7 g of acrylamide
(0.33 m) in 300 g of H.sub.2 O. The monomers were then charged to a
3-liter resin flask equipped with an air-driven stirrer, condenser,
thermocouple and N.sub.2 inlet. After purging the system with
N.sub.2, 4.61 g of ammonium persulfate (0.02 m) in 100 g of
deionized H.sub.2 O was added along with 0.023 g of FeSO.sub.4 (100
ppm) in 10 g of deionized H.sub.2 O. Additional deionized H.sub.2 O
was charged to the flask to bring the solids concentration to 10%
(w/w). The solution was heated for 4 hours at 82.+-.2.degree. C.
After 2 hours, 6.86 g of NaHSO.sub.3 (0.065 m) and 2.74 g of
(NH.sub.4).sub.2 S.sub.2 O.sub.8 (0.012 m) were added. One hour
later, 1.38 g of NaHSO.sub.3 (0.013 m) was added.
EXAMPLE 8
32 g of NaOH (0.8 m) was dissolved in 1200 g of deionized H.sub.2
O. 165.6 g of AMPS (0.8 m) was added to the NaOH solution, with
cooling. 56.8 g of acrylamide (0.8 m) was dissolved in 300 ml of
deionized H.sub.2 O and added to the AMPS solution. The monomers
were then charged to a 3-liter resin flask equipped with an
air-driven stirrer, condenser, N.sub.2 inlet and thermocouple. The
system was purged with N.sub.2. 4.45 g of (NH.sub.4).sub.2 S.sub.2
O.sub.8 (0.02 m) and 0.0389 g of FeCl.sub.3 (175 ppm) were added to
the solution, along with deionized H.sub.2 O to bring the solids
content to 10% (w/w). The solution was heated to 82.degree. C. and
maintained for 4 hours. After 2 hours at 82.degree. C., 8.32 g of
NaHSO.sub.3 (0.08 m) was added and after 3 hours, 1.66 g of
NaHSO.sub.3 (0.016 m) was added.
EXAMPLE 9
14.37 g of AMPS (0.069 m) was neutralized with 2.8 g NaOH (0.069 m)
predissolved in 150 ml of deionized H.sub.2 O. 44.0 g of acrylamide
(0.63 m) was dissolved in 150 g of H.sub.2 O. The two monomer
solutions were mixed and added to a 1-liter resin kettle equipped
with reflux condenser, stirrer, N.sub.2 purge, and thermocouple.
After N.sub.2 purging, 1.18 g of (NH.sub.4).sub.2 S.sub.2 O.sub.8
(0.005 m) predissolved in 70 ml deionized H.sub.2 O and 0.018 g of
FeCl.sub.3 (300 ppm) predissolved in 70 ml deionized H.sub.2 O were
added at room temperature. The reaction temperature was slowly
raised to 80.degree. C. and an additional 250 ml of deionized
H.sub.2 O added to the reaction. After 2 hours, the reaction was
stopped. The product was a clear, very viscous liquid, 7.7 wt %
solids.
EXAMPLE 10
82.8 g of AMPS (0.4 m) dissolved in 200 ml deionized H.sub.2 O was
neutralized with 16 g of NaOH (0.4 m) and charged to a 500 ml
4-neck resin kettle equipped with a stirrer, reflux condenser,
thermocouple, and N.sub.2 purge. To this mixture, 3.8 g of vinyl
acetamide (ACE) (0.045 m) dissolved in 58 ml of H.sub.2 O and 0.87
g of AIBN (0.1 phm) dispersed in 30 ml of H.sub.2 O were added with
stirring. The reaction mixture was N.sub.2 purged and its
temperature raised to 92.degree. C. and maintained for 3 hours.
Infrared spectrum and C, H, N substantiated a 9/1 comonomer ratio
in the polymer.
EXAMPLE 11
After cooling, 124 g of the aqueous polymer solution of
poly(AMPS-(co)-ACE) (0.013 m ACE) of Example 10 was charged into a
500 ml round bottom flask with condenser and 2.64 ml of 37% aq. HCl
(0.0267 m) was added. The solution was refluxed for 20 hours. The
resulting product was a pale yellow-green liquid containing 10%
poly(AMPS-(co)-vinylamine) by weight. Infrared spectrum
substantiates hydrolysis to the title polymer.
EXAMPLE 12
54.03 g of AMPS (0.26 m) was neutralized with 10.44 g of NaOH (0.26
m) predissolved in 240 ml of deionized H.sub.2 O. To a 1500 ml
resin kettle fitted with the standard equipment was added the AMPS
monomer solution, 200 g of vinylacetamide (2.35 m) predissolved in
340 ml of deionized H.sub.2 O. To a 1500 ml resin kettle fitted
with the standard equipment was added the AMPS monomer solution,
200 g of vinylacetamide predissolved in 340 ml of deionized H.sub.2
O, and 2.54 g of azobis-isobutyronitrile (0.0132 m) predissolved in
40 ml of ethyl acetate. After N.sub.2 purging, the reaction
temperature was raised to 85.degree. C. and maintained for 3 hours.
The product was precipitated into acetone and dried in vacuo at
43.degree. C. overnight. A white powder was obtained. Infrared
spectrum confirmed copolymerization.
EXAMPLE 13
442.8 g of the 30% solids solution of Example 12 (1.36 m ACE) and
29.26 g of 37% HCl (2.9 m) were charged into a 1000 ml round bottom
flask equipped with a reflux condenser and refluxed for 22 hours.
The polymeric product was precipitated into acetone and dried in
vacuo at 45.degree. C. for 24 hours. A brown solid polymer was
obtained. Infrared spectrum confirmed hydrolysis.
EXAMPLE 14
To a 500 ml resin kettle equipped with reflux condenser, stirrer,
N.sub.2 purge, and thermocouple was charged 20 g of AMPS (0.097 m),
13.9 g of acrylic acid (0.193 m), and 40 ml of deionized H.sub.2 O.
To this mixture was added 1.02 g of (NH.sub.4).sub.2 S.sub.2
O.sub.8 (0.0045 m) predissolved in 10 ml of H.sub.2 O, 0.003 g of
FeSO.sub.4.7H.sub.2 O (2.2.times.10.sup.-6 m) predissolved in 15 ml
of H.sub.2 O. The reactants were N.sub.2 purged for 5 minutes with
stirring. After 15 minutes at room temperature (22.degree. C.), the
reaction exothermed to a maximum temperature of 41.degree. C. After
2 hours, the reaction was terminated leaving a clear viscous
polymer solution of 30% solids. Infrared spectrum and percent
conversion data confirmed a 2/1 mole comonomer ratio in the
resultant polymer.
EXAMPLE 15
A 2-liter resin kettle was fitted with a paddle stirrer, condenser,
N.sub.2 inlet and 100 ml dropping funnel. 83 g of PVP K-90 (0.75 m)
from GAF (nominal mol. wt. 360,000) was dissolved in one liter of
distilled water. 52 g of AMPS monomer (0.25 m) was added to this
solution, stirred to dissolve and transferred to the resin kettle.
The contents were then purged with N.sub.2 and gently stirred for
45 minutes.
The ceric ion catalyst solution was prepared by dissolving 0.140 g
of ceric ammonium nitrate in 100 ml of deionized H.sub.2 O
containing 2.5 ml of one normal nitric acid. This catalyst was
transferred to a dropping funnel and then added, by drops, to the
reaction solution at 23.degree. C. over a one hour period. After
stirring overnight, the viscous solution was added to a ten-fold
excess of acetone and a white-rubbery solid was precipitated. The
precipitate was broken up into small pieces, washed with acetone
and dried overnight at 60.degree. C. in vacuum. The resulting
solids were crushed by hand to a fine powder, washed with acetone,
isolated by filtration and dried in vacuo at 56.degree. C.
overnight to afford 113 g of PVP-b-AMPS triblock polymer (84%
conversion). The molecular weights of the AMPS end blocks and the
PVP center block were calculated according to the procedure
described in U.S. Pat. No. 3,993,712 and found to be
1.times.10.sup.5 and 3.6.times.10.sup.5, respectively.
EXAMPLE 16
Six individual molecular weights of polymers containing ethoxylated
amine salts of sulfonic acid were synthesized by varying initiator
and chain transfer agent concentrations. The procedure was as
follows:
16A. A one liter resin kettle with overhead stirrer, N.sub.2 inlet,
condenser, thermocouple, heating mantel, and provision for external
cooling was set up in a hood.
24.5 g of AMPS (0.118 m) was dissolved in 118 ml of 1N NaOH and the
pH adjusted to 8, the total weight was 159.3 g. This solution was
then added to the kettle along with 152.8 g of 49.4%. Dow aqueous
acrylamide (1.06 m) and 100 ml of H.sub.2 O. Then 0.038 g of
CuCl.sub.2.2H.sub.2 O dissolved in 62 ml of H.sub.2 O was added.
Heating, stirring, and N.sub.2 purging was performed.
After about 40 minutes when after reaching a temperature of
50.degree. C., the heating mantle was removed and 0.50 g of
(NH.sub.4).sub.2 S.sub.2 O.sub.8 dissolved in 25 ml of H.sub.2 O
was added, the temperature fell to 46.degree.-47.degree. C. Within
5 minutes the exotherm started, the solution became thicker, and
the N.sub.2 flow was reduced and removed to the head space. The
calculated heat of polymerization at room temperature was
22.5.degree. C., based on a 25% aqueous acrylamide solution.
External cooling was applied to maintain the temperature at or
below 60.degree. C. After completion of the exotherm, a temperature
of 50.degree. C. was maintained. A sample was removed after 2 hours
for acrylamide analysis, the nitrogen turned off, and 0.63 g of
NaHSO.sub.3 (0.5 mole % based on acrylamide) dissolved in 25 ml of
H.sub.2 O was added. After stirring for an hour, vacuum was pulled
for 1-3 minutes several times over about a 15 minute period to help
remove excess SO.sub.2. While stirring vigorously, 118 g (0.059 m)
of soyabis (polyoxyethylene).sub.15 amine was added with 75 ml of
wash H.sub.2 O over about 15 minutes period. After the additions,
the pH was 8. Citric acid solution (25 g) was added to lower the pH
to 6.+-.0.5. The intrinsic viscosity of the polymer-sodium salt was
1.04 dl/g measured in 5.05N NaCl at 29.degree. C.
The following additional materials were also prepared by the above
described procedure. All intrinsic viscosities were measured on the
sodium salt form of the polymer.
EXAMPLE NO.
Examples 16B, C, D, E and F had intrinsic viscosities of 0.875
dl/g, 1.22 dl/g, 2.15 dl/g, 7.1 dl/g and 8.55 dl/g, respectively.
The final product of Examples 16 B, C, D, E and F was the soya
bis(polyethylene).sub.15 amine salt as specified in Example
16A.
EXAMPLE 17
This Example was prepared by the method of Example 16 except that
236 g (0.118 m) of soya bis (polyoxyethylene).sub.15 amine was
added instead of 118 g.
EXAMPLE 18
This Example was prepared by the method of Example 16 except that
55.17 g (0.059 m) of cetyl-stearyl bis (polyoxyethylene).sub.7.5
amine was added instead of 118 g of soya bis
(polyoxyethylene).sub.15 amine.
EXAMPLE 19
This Example was prepared by the method of Example 16 except that
145.73 g (0.059 m) of cetyl-stearyl bis (polyoxyethylene).sub.25
amine was added instead of 118 g of soya bis
(polyoxyethlene).sub.15 amine.
EXAMPLE 20
This Example was prepared by the method of Example 16 except that
291.46 g (0.118 m) of cetyl-stearyl bis (polyoxyethylene).sub.25
amine was added instead of 118 g of soya bis
(polyoxyethylene).sub.15 amine.
EXAMPLE 21
This Example was prepared by the method of Example 16 except that
55.17 g (0.059 m) of tallow bis (polyoxyethylene).sub.7.5 amine was
added instead of 118 g of soya bis (polyoxyethylene).sub.15
amine.
EXAMPLE 22
This Example was prepared by the method of Example 16 except that
110.33 g (0.118 m) of tallow bis(polyoxyethylene).sub.7.5 amine was
added instead of 118 g soya bis(polyoxyethylene).sub.15 amine.
EXAMPLE 23
This Example was prepared by the method of Example 16 except that
54.87 g (0.059 m) of stearyl bis(polyoxyethylene).sub.7.5 amine was
added instead of 118 g soya bis(polyoxyethylene).sub.15 amine.
EXAMPLE 24
This Example was prepared by the method of Example 16 except that
145.73 g (0.059 m) of stearyl bis(polyoxyethylene).sub.25 amine was
added instead of 118 g soya bis(polyoxyethylene).sub.15 amine.
EXAMPLE 25
This Example was prepared by the method of Example 16 except that
291.46 g (0.118 m) of steary bis(polyoxyethylene).sub.25 amine was
added instead of 118 g of soya bis(polyoxyethylene).sub.15
amine.
EXAMPLE 26
This Example was prepared by the method of Example 16 except that
52.22 g (0.059 m) of coco bis(polyoxyethylene).sub.7.5 amine was
added instead of 118 g of soya bis(polyoxyethylene).sub.15
amine.
EXAMPLE 27
This Example was prepared by the method of Example 16 except that
73.46 g (0.059 m) of an ethoxylated amine having the structure
shown below was added instead of 118 g of soya bis
(polyoxyethylene).sub.15 amine. ##STR13##
EXAMPLE 28
This Example was prepared by the method of Example 16 except that
146.92 g (0.18 m) of an ethoxylated amine having the structure
shown below was added instead of 118 g of soya bis
(polyoxyethylene).sub.15 amine. ##STR14##
EXAMPLE 29
20 g of a poly(2-acrylamido-2-methyl propane sodium sulfonate) 0.09
m) (Example 1) dissolved in 37 g of water was adjusted to pH 4.0
with citric acid. 66 g soya bis(polyoxyethylene).sub.15 amine
(0.045 m) was then reacted and the pH adjusted to 6.5.
EXAMPLE 30
20 g of a solution of 35% by weight 2-acrylamido 2-methyl propane
sodium sulfonate (0.03 m) (Example 1) adjusted to pH 6 with NaOH,
was reacted while mixing with 15.3 g of methyl
polyoxyethylene.sub.(15) octadecylammonium chlorde (0.015 m).
Each of the neutralized sulfonic acid-containing polymers prepared
in the above Examples was evaluated as a hair conditioner.
Specifically, each polymer was evaluated with respect to the
following properties: wet/dry combing, feel, curl retention, and
static fly away. All polymers were evaluated in a model conditioner
and shampoo/conditioner formulation. The test procedures are set
forth below and the respective results are recorded in Tables
I-V.
Each polymer as well as a selection of commercial additives were
evaluated sequentially for wet and dry combability and feel in
model conditioner and shampoo/conditioner. Performance was
evaluated by independent observers on coded samples using a rating
of 1 to 10 (poor to excellent).
A separate 2 gram swatch was used for each product. The 8" dark
brown virgin hair was obtained from DeMeo Bros., 39 W. 28th St.,
New York, N.Y. 10001. The swatch was immersed in the model
formulation solution for 1 minute, rinsed with running tap water
for 5 seconds, and dunked 10 times in distilled water. The swatch
was subsequently evaluated as follows:
Combability--Wet:
The swatch was combed wet and rated for ease of combing.
Combability--Dry:
After wet combing, the swatch was air dried, combined and rated
again for ease of combining.
Feel:
After dry combing, each swatch was evaluated for feel by two (2)
people and rated.
The above test sequence was repeated four (4) times on the swatch
for each material tested. The results shown in Tables I and II are
expressed as an average of these ratings.
Examples 16 through 25 were evaluated using a rating of 1 to 10 for
dry combability and feel; however, wet combability was assessed in
a different manner from the previous examples (1-15). The time in
seconds were recorded in which it took to completely detangle each
wet swatch; the less the time, the better the detangling ability of
the conditioner. In order to record a meaningful detangling time, 3
of 18" dark brown virgin hair was used for each swatch. The results
shown in Tables III and IV are given as an average of wet comb
times expressed in seconds. Dry combability and feel are expressed
as ratings (1-10) for two swatches tested 4 times each.
Following completion of the comb and feel tests, the hair swatches
were evaluated for curl retention as follows:
The dry swatch was dipped in water, curled wet on 1/2-inch diameter
rollers and air dried. It was then placed in a humidity chamber set
at 85% RH, 72.degree. F. The curler was removed upon placement in
the chamber. After 1 hour exposure, the length of the hair swatch
was measured and curl retention calculated using the equation
below.
Additionally, each product was tested as a setting gel. Upon
completion of the above curl retention test, each dry swatch was
dipped into the conditioning formulation for 90 seconds, curled on
a 1/2-inch roller and air dried. It was then placed in the
aforementioned humidity chamber. After 1 hour exposure, the hair
swatch length was measured. The percent curl retention was
calculated using the equation below (Table V). ##EQU1##
It should be mentioned that all test methods are subject to human
appraisal and thus should be considered to give subjective results
although every effort was made to insure unbiased opinions. The
data are qualitative rather than quantitative.
Examples 1-15 are considered to depict various Sulfonic Acid
containing polymers that have not been neutralzied with an
alkoxylated nitrogen containing salt and, hence, represent a basis
from which to evaluate the effect of neutralization in accordance
with this invention. Example 16A was made in accordance with this
invention and demonstrates a clear overall superiority over alkali
metal (Na) neutralized polymers with respect to the conditioning
properties.
Curl retention, in some cases, was demonstrated to be at least as
good as the comparative commercial products.
These results are listed in Tables I, II and V. Tables III and IV
contain additional test data for polymers of the invention. It is
also pointed out that the polymer of the invention has been
contrasted with seven commercially available polymers. As in the
comparison with the alkali metal neutralized polymers, the polymer
of the invention possesses a clear general superiority in relevant
hair care properties. The commercially available polymers are
discussed further in Table VI.
TABLE I
__________________________________________________________________________
Performance in a Model Conditioner.sup.a Material Tested pH Wet
Comb Dry Comb Feel Fly Away Control
__________________________________________________________________________
Example 1 6 6.1 7.9 6.3 Excellent Example 2 6 5.7 7.5 6.3 Excellent
Example 2S.sup.b 6 7.5 8.6 6.8 Excellent Example 3 11.0 5.8 8.0 7.0
Good Example 4 11.2 7.8 8.0 7.3 Good Example 5 8.6 7.3 8.0 4.6 Good
Example 6 6 8.6 7.9 7.5 Excellent Example 7 6 8.9 7.9 6.6 Excellent
Example 8 6 7.5 7.9 7.0 Excellent Example 9 6 8.2 7.5 7.0 Excellent
Example 10 6 6.4 6.8 6.1 Excellent Example 11 7.4 6.5 8.0 5.6 Good
Example 12 6 7.5 6.4 5.5 Good Example 13 6 4.3 6.1 4.1 Average
Example 15 6 5.7 7.1 6.6 Good Example 16A 6 9.0 8.0 8.0 Excellent
Polymer JR 6 7.1 7.9 5.7 Poor Stearylalkonium Chloride 6 7.9 7.5
6.8 Average Flexan 130 6 8.5 8.5 5.1 Excellent Merquat 550 6 7.3
8.8 6.4 Average GAF 550 6 9.3 8.3 6.0 Poor PVP (K-90) 6 7.3 9.0 6.0
Poor Carbopol 940 6 7.3 8.3 7.0 Good Blank 6 6.2 7.2 5.5 Average
__________________________________________________________________________
.sup.a Formulation: 0.5 parts Polymer or Commercial additive 99.5
parts Distilled Water pH adjusted with HCl or NaOH .sup.b Stearyl
benzyl dimethyl ammonium salt of poly (AMPS) from Example 2.
TABLE II ______________________________________ Performance in a
Model Shampoo/Conditioner.sup.a Material Tested pH Wet Comb Dry
Comb Feel ______________________________________ Example 1 6 6.8
6.8 7.3 Example 2 6 6.8 7.9 7.3 Example 2S 6 7.5 7.9 7.7 Example 3
7.5 5.0 8.0 5.3 Example 4 9.0 8.0 8.0 5.3 Example 5 8.5 5.0 8.0 6.5
Example 6 6 6.1 7.1 7.9 Example 7 6 6.1 7.5 7.5 Example 8 6 5.7 7.9
6.8 Example 9 6 9.3 8.6 7.3 Example 10 6 5.7 7.9 8.0 Example 11 7.4
7.3 8.0 6.4 Example 12 6 7.5 7.5 7.9 Example 13 6 6.4 8.2 6.6
Example 14 8.5 4.5 8.0 6.5 Example 15 6 5.4 7.1 7.7 Example 16
A.sup.b 6 8.5 8.7 8.0 Polymer JR 6 8.9 8.6 7.3 Stearylalkonium
Chloride 6 5.4 7.1 7.5 Flexan 130 6 6.3 8.5 7.8 Merquat 550 6 8.5
9.0 8.3 GAF 755N 6 5.3 8.8 7.4 PVP (K-90) 6 7.0 8.8 7.4 Carbopol
940 6 5.8 8.8 8.1 Blank 6 6.2 6.2 6.4
______________________________________ .sup.a Formulation: 0.5
parts Polymer or Commercial Additive, 12.5 parts Ammonium Lauryl
Sulfate, 87.0 parts Distilled Water, pH adjusted with HCl or NaOH
.sup.b Hair tested was 18 inch, dark brown virgin hair.
TABLE III ______________________________________ Performance of
Ethoxylated Polymers in Model Conditioner.sup.a Wet Comb Dry Comb
Feel Material Tested (sec.) (1-10) (1-10)
______________________________________ Example 16A 9.1 9.3 8.3
Example 16B 5.1 8.7 8.3 Example 16C 5.9 9.5 8.7 Example 16D 6.9 9.3
8.3 Example 16E 22.0 8.3 7.7 Example 16F 3.9 9.2 7.6 Example 17 6.2
9.7 8.3 Example 18 8.7 6.9 7.4 Example 19 9.7 8.4 7.9 Example 20
8.1 9.3 8.3 Example 21 10.5 9.0 7.3 Example 22 7.2 8.7 7.9 Example
23 9.5 7.5 7.3 Example 24 18.5 8.3 8.4 Example 25 18.3 8.9 7.7
Example 26 8.7 6.1 7.9 Example 29 12.7 9.0 8.2 Example 30 10.8 9.3
7.9 Blank 16.5 7.9 7.7 ______________________________________
.sup.a Formulation: 0.5 parts polymer 99.5 parts distilled water pH
adjusted to 6.0 .+-. .2 with citric acid or NaOH
TABLE IV ______________________________________ Performance of
Ethoxylated Polymers in Model Conditioning Shampoo.sup.a Wet Comb
Dry Comb Feel Material Tested (sec.) (1-10) (1-10)
______________________________________ Example 16A 22.4 8.7 8.0
Examp1e 16B 35.9 8.1 7.6 Example 16C 22.5 9.2 8.7 Example 16D 22.4
8.7 8.0 Example 16E 28.4 8.7 7.8 Example 16F 36.8 8.2 7.7 Example
17 29.5 8.7 7.9 Example 18 38.1 6.3 7.9 Example 19 48.8 8.4 7.7
Example 20 37.8 8.8 8.3 Example 21 41.9 8.2 7.7 Example 22 34.8 8.4
7.6 Example 23 48.6 6.3 7.7 Example 24 54.3 7.9 7.8 Example 25 29.3
7.6 7.7 Example 26 49.4 6.5 7.5 Example 27 39.5 8.75 8.4 Example 28
30.8 7.8 8.3 Example 29 49.2 7.5 7.9 Example 30 51.7 7.9 7.4 Blank
51.6 7.3 7.5 ______________________________________ .sup.a
Formulation: 0.5 parts polymer 12.5 parts ammonium lauryl sulfate
87 parts distilled water pH adjusted to 6.sup..+-. 0.2 with citric
acid or NaOH
TABLE V
__________________________________________________________________________
Curl Retention Curl Retention on Model.sup.b Curl Retention.sup.a
Curl Retention.sup.a Material Tested Shampoo/Conditioner In
Conditioner In Setting Gel
__________________________________________________________________________
Example 1 7.7% 7.7% 11.5% Example 2 15.4% 15.4% 26.9% Example 2S
19.2% 11.5% 11.5% Example 3 29.0% 18.0% -- Example 4 18.0% 23.5% --
Example 5 32.0% 28.0% -- Example 6 15.4% 15.4% 19.2% Example 7
19.2% 19.2% 19.2% Example 8 23.1% 15.4% 15.4% Example 9 15.4% 19.2%
80.8% Example 10 19.2% 11.5% 7.7% Example 11 22.0% 29.0% -- Example
12 15.4% 30.8% 15.4% Example 13 19.2% 11.5% 26.9% Example 15 15.7%
7.7% 11.5% Example 16 15.0% 15.0% -- Example 29 17.8% 14.3% --
Polymer JR 15.4% 26.9% 92.3% Stearylalkonium Chloride 19.2% 26.9%
23.1% Flexan 130 15.4% 7.7% 15.4% Merquat 550 21.7% 11.5% 30.8% GAF
755N 11.5% 19.2% 19.2% PVP (K-90) 26.1% 30.8% 19.2% Carbopol 940
11.5% 30.8% 88.5% Blank 19.2% 15.4% 15.4%
__________________________________________________________________________
.sup.a Formulation: 0.5 parts Polymer or Commercial Additive, 99.5
parts Distilled Water, pH Adjusted with HCl or NaOH .sup.b
Formulation: 0.5 parts Polymer or Commercial Additive, 12.5 parts
Ammonium Lauryl Sulfate, 87.0 parts Distilled Water, pH Adjusted
with HCl or NaOH
TABLE VI ______________________________________ POLYMER DESCRIPTION
______________________________________ Polymer JR quaternary
nitrogen-containing hydroxyethyl cellulose Stearylalkonium Chloride
stearyl benzyl dimethyl ammonium chloride Flexan 130 sodium
poly(styrene sulfonate) Merquat 550 poly(acrylamide-(co)-diallyl
dimethyl ammonium chloride) GAF 775N poly(vinyl pyrrolidone-(co)-
dimethyl amino ethyl methacrylate) PVP (K-90) poly(vinyl
pyrrolidone) 360,000 mol. wt. Carbopol 940 lightly crosslinked
poly(acrylic acid) ______________________________________
* * * * *